N-phenoxphenyloxymethyl substituted azoles and method for controlling pests therewith

ABSTRACT

N-substituted azoles of the formula I ##STR1## where R 1 , R 2 , R 3  are each hydrogen, halogen, C 1  -C 8  -alkyl, C 1  -C 8  -alkoxy, C 1  -C 4  -haloalkyl, C 1  -C 4  -haloalkoxy, C 3  -C 10  -cycloalkyl, nitro or cyano, 
     Q is an unsubstituted or substituted azole group of the formulae IIa-IIf ##STR2## R 4  to R 15  denoting hydrogen, halogen, C 1  -C 8  -alkyl, C 1  -C 4  -haloalkyl, C 1  -C 4  -alkoxy, C 3  -C 10  -cycloalkyl or aryl which is unsubstituted or mono-, di- or trisubstituted by halogen, C 1  -C 8  -alkyl, C 1  -C 8  -alkoxy, C 1  -C 4  -haloalkyl or C 1  -C 4  -haloalkoxy, and 
     X is, in the case of the azole group IIa, --CH 2  -- or --O(CH 2 ) n  --, n being one of the integers 1, 2 or 3, or, in the case of the azole groups IIb-IIf, --OCH 2  --, 
     pesticides containing compounds I as active ingredients, and a process for combating pests.

This is a division of application Ser. No. 07/516,925, filed on Apr. 30,1990, now U.S. Pat. No. 5,116,860, which is a division of Ser. No.07/184,804, filed Apr. 22, 1988, now U.S. Pat. No. 4,943,585.

The present invention relates to novel N-substituted azoles of thegeneral formula: ##STR3## where R¹, R² and R³ are each hydrogen,halogen, C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄-haloalkoxy, C₃ -C₁₀ -cycloalkyl, nitro or cyano, Q is an unsubstitutedor substituted azolyl radical of the formulae IIa-IIe ##STR4## where R⁴to R¹⁵ are each hydrogen, halogen, C₁ -C₈ -alkyl, C₁ -C₄ -haloalkyl, C₁-C₄ -alkoxy, C₃ -C₁₀ -cycloalkyl or aryl which is unsubstituted ormonosubstituted to trisubstituted by halogen, C₁ -C₈ -alkyl, C₁ -C₈-alkoxy, C₁ -C₄ -haloalkyl or C₁ -C₄ -haloalkoxy, and X is --CH₂ -- or--O(CH₂)_(n) --, where n is 1, 2 or 3, in the case of the azolyl radicalIIa and is --OCH₂ -- in the case of the azolyl radicals IIb-IIf.

The present invention furthermore relates to pesticides which containthe compounds I as active ingredients, and a method for controllingpests.

EP-A-132 606 discloses N-substituted azoles as insecticidal andacaricidal active ingredients. However, the action of these compounds isunsatisfactory.

It is an object of the present invention to provide novel N-substitutedazoles I having an improved action.

We have found that this object is achieved by the novel N-substitutedazoles I defined at the outset. We have also found that the compounds Iare very suitable for controlling pests.

The compounds I are obtainable by the following methods:

a) For the preparation of the compounds I in which X is --CH₂ --, ap-phenoxybenzyl compound III is reacted with an anion of an imidazole IVin accordance with the following equation: ##STR5##

Some of the p-phenoxybenzyl compounds III are known from the literature(for example from GB-A-1 140 748, DE-A-24 18 572 and EP-A-132 606);those which are unknown can be prepared in a conventional manner.

The anions of the imidazoles IV can be generated from imidazoles IVawhich are known from the literature or are commercially available, by aconventional method, in the form of the corresponding salts, such as thesodium or potassium salt.

The compounds Ia can also be obtained by reacting III with an imidazoleIVa ##STR6## in the presence of a base. Not less than equivalent amountsof a base are usually added to III and/or IVa, although these may alsobe used in excess or, as the case may be, even as a solvent. Examples ofsuitable bases are alcoholates of alkali metals, such as sodiummethylate, sodium ethylate or potassium tert-butylate, alkali metal oralkaline earth metal hydrides, such as sodium hydride, potassium hydrideor calcium hydride, alkali metal carbonates, such as sodium carbonate orpotassium carbonate, aliphatic amines, such as dimethylamine,triethylamine or diisopropylamine, heterocyclic amines, such aspiperidine, piperazine or pyrrolidine, aromatic amines, such as pyridineor pyrrole, and, if required, also alkyllithium compounds, such asn-butyllithium.

b) For the preparation of the compounds I in which X is --O(CH₂)₂ -- or--O(CH₂)₃ --, a p-phenoxyphenoxy compound V is reacted with an anion ofan imidazole IV in accordance with the following equation: ##STR7##

c1) For the preparation of the compounds I in which X is --OCH₂ --, ap-phenoxyphenol VI is reacted with an N-methylazole VII in the presenceof a base at from -20° to 250° C., preferably from 20° to 120° C., inaccordance with the following equation: ##STR8##

Some of the p-phenoxyphenols VI are disclosed in Houben-Weyl, Vol. VI,3, Methoden der org. Chemie, Thieme Verlag, 1965, 585 et seq.; thosewhich are not known can be prepared by the methods described there.

Some of the N-methylazoles VII are disclosed in Heterocycles 24 (1986),2233; those which are not known can be prepared by the method describedthere, in accordance with the following equation: ##STR9##

c2) For the preparation of the compounds I in which X is --OCH₂ --, aphenolate anion of VI is reacted with an N-methylazole VII at from -20°to 120° C., preferably from -20° to 80° C., in accordance with thefollowing equation: ##STR10##

The p-phenoxyphenolate anions VI are known in the form of their metalsalts, such as the sodium or potassium salt, or can be generated fromthe p-phenoxyphenols by reaction with conventional metallizationreagents, such as sodium methylate, sodium ethylate, potassiumtert-butylate, sodium hydride, potassium hydride or butyllithium.

In all four embodiments, Z is a leaving group, for example a sulfonicacid radical or a halogen. Preferred sulfonic acid radicals aremethanesulfonyl, trifluoromethanesulfonyl and p-toluenesulfonyl, andpreferred halogens are chlorine and bromine, chlorine being particularlypreferred.

The reactions of the particular anions of the metal salts in cases a),b), c1) and c2) are advantageously carried out in a solvent or diluent.For example, aliphatic hydrocarbons, such as n-pentane, n-hexane, amixture of hexaneisomers, petroleum ether, cyclohexane or heptane,aromatic hydrocarbons, such as benzene, toluene, the xylenes and theirisomer mixtures, gasoline, chlorohydrocarbons, such as methylenechloride, chloroform, carbon tetrachloride or 1,2-dichloromethane,chlorinated aromatics, such as chlorobenzene or 1-chloronaphthalene,ethers, such as diethyl ether, di-n-butyl ether, methyl tert-butylether, tetrahydrofuran or dioxane, ketones, such as acetone, methylethyl ketone or methyl isopropyl ketone, nitriles, such as acetonitrileor propionitrile, and aprotic dipolar solvents, such asdimethylformamide, dimethyl sulfoxide or pyridine, are suitable for thispurpose. Mixtures of these substances can also be used as solvents ordiluents.

For the preparation of the novel compounds I by the methods describedabove, the starting materials are usually used in a stoichiometricratio. However, an excess of one or other of the starting materials maybe very advantageous in specific cases.

The reactions usually take place at an adequate rate above -30° C. Ingeneral, 100° C. must not be exceeded. Since they take place withevolution of heat in some cases, it may be advantageous to provide ameans of cooling.

The reaction mixtures are worked up in a conventional manner, forexample by the addition of water, separation of the phases and columnchromatography. Some of the novel compounds of the formula I areobtained in the form of a colorless or pale brownish, viscous oil, whichcan be freed from the last volatile components by prolonged heating atmoderately elevated temperatures under reduced pressure and can bepurified in this manner. If the compounds of the formula I are obtainedin crystalline form, they may be purified by recrystallization.

The substituents in formula I have the following specific meanings: R¹is hydrogen, halogen, preferably fluorine, chlorine or bromine,particularly preferably fluorine or chlorine in the meta-position,straight-chain or branched C₁ -C₈ -alkyl, preferably straight-chain orbranched C₁ -C₆ -alkyl, particularly preferably straight-chain orbranched C₁ -C₄ -alkyl in the meta-position, such as m-methyl, m-ethyl,m-(n-propyl), m-isopropyl, m-(n-butyl), m-isobutyl, m-(sec-butyl) andm-(tert-butyl), straight-chain or branched C₁ -C₈ -alkoxy, preferablystraight-chain or branched C₁ -C₄ -alkoxy, particularly preferably C₁ -or C₂ -alkoxy in the meta-position, such as m-methoxy or m-ethoxy,straight-chain or branched C₁ -C₄ -haloalkyl, preferably C₁ - or C₂-fluoro- or chloroalkyl, particularly preferably m-trifluoromethyl orm-trichloromethyl, straight-chain or branched C₁ -C₄ -haloalkoxy,preferably C₁ -or C₂ -fluoro-or chloroalkoxy, particularly preferablym-trifluoromethoxy or m-trichloromethoxy, C₃ -C₁₀ -cycloalkyl,preferably C₃ -C₆ -cycloalkyl, particularly preferably m-cyclopropyl,m-cyclobutyl, m-cyclopentyl or m-cyclohexyl, nitro or cyano, R² and R³independently of one another are each hydrogen, halogen, preferablyfluorine or chlorine, straight-chain or branched C₁ -C₈ -alkyl,preferably straight-chain or branched C₁ -C₄ -alkyl, particularlypreferably C₁ - or C₂ -alkyl, such as methyl or ethyl, straight-chain orbranched C₁ -C₈ -alkoxy, preferably straight-chain or branched C₁ -C₄-alkoxy, particularly preferably C₁ - or C₂ -alkoxy, such as methoxy orethoxy, straight-chain or branched C₁ -C₄ -haloalkyl, preferably C₁ - orC₂ -fluoro- or chloroalkyl, particularly preferably trifluoromethyl ortrichloromethyl, straight-chain or branched C₁ -C₄ -haloalkoxy,preferably C₁ - or C₂ -fluoro- or chloroalkoxy, particularly preferablytrifluoromethoxy or trichloromethoxy, C₃ -C₁₀ -cycloalkyl, preferably C₃-C₆ -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl orcyclohexyl, particularly preferably cyclopropyl, nitro or cyano, R⁴ toR¹⁵ independently of one another are each hydrogen, halogen, preferablyfluorine or chlorine, straight-chain or branched C₁ -C₈ -alkyl,preferably straight-chain or branched C₁ -C₄ -alkyl, particularlypreferably C₁ - or C₂ -alkyl, such as methyl or ethyl, straight-chain orbranched C₁ -C₄ -haloalkyl, preferably C₁ - or C₂ -fluoro, chloroalkyl,particularly preferably trifluoromethyl or trichloromethyl,straight-chain or branched C₁ -C₈ -alkoxy, preferably straight-chain orbranched C₁ -C₄ -alkoxy, particularly preferably C₁ - or C₂ -alkoxy,such as methoxy or ethoxy, C₃ -C₁₀ -cycloalkyl, preferably C₃ -C₃-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,particularly preferably cyclopropyl, aryl, preferably phenyl, 1-naphthylor 2-naphthyl, particularly preferably phenyl, aryl which ismonosubstituted to trisubstituted by halogen, preferably phenyl which ismonosubstituted by fluorine or chlorine, such as 2-fluorophenyl,3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl or4-chlorophenyl, aryl which is monosubstituted to trisubstituted bystraight-chain or branched C₁ -C₈ -alkyl, preferably phenyl which ismonosubstituted by straight-chain or branched C₁ -C₄ -alkyl,particularly preferably phenyl which is monosubstituted by C₁ - or C₂-alkyl, such as 4-methylphenyl or 4-ethylphenyl, aryl which ismonosubstituted to trisubstituted by straight-chain or branched C₁ -C₈-alkoxy, preferably phenyl which is monosubstituted by straight-chain orbranched C₁ -C₄ -alkoxy, particularly preferably phenyl which ismonosubstituted by C₁ - or C₂ -alkoxy, such as 4-methoxyphenyl or4-ethoxyphenyl, aryl which is monosubstituted to trisubstituted bystraight-chain or branched C₁ -C₄ -haloalkyl, preferably phenyl which ismonosubstituted by C₁ - or C₂ -fluoro- or chloroalkyl, particularlypreferably phenyl which is monosubstituted by trifluoromethyl ortrichloromethyl, such as 4-trifluoromethylphenyl or4-trichloromethylphenyl, aryl which is monosubstituted to trisubstitutedby straight-chain or branched C₁ -C₄ -haloalkoxy, preferably phenylwhich is monosubstituted by C₁ - or C₂ -fluoro- or chloroalkoxy,particularly preferably phenyl which is monosubstituted bytrifluoromethoxy or trichloromethoxy, such as 4-trifluoromethoxyphenylor 4-trichloromethoxy, such and X is --CH₂ --, --OCH₂ --, --O(CH₂)₂ --or --O(CH₂)₃ --.

In contrast to most of the active ingredients known to date, which actas contact or ingested poisons and kill, incapacitate or repel theanimals, most of the compounds of the formula I interfere with thedevelopment of the animal organism. In the case of insects, for example,the transformation to the imago, the laying of viable eggs and thedevelopment of normal laid eggs are disturbed and the sequence ofgenerations thus interrupted. The active ingredients according to theinvention are virtually completely non-toxic for vertebrates. Moreover,most the compounds of the formula I are readily degraded to substanceswhich occur in nature and are further decomposed by microorganisms.

The N-substituted azoles of the general formula I are suitable foreffectively combating pests from the class consisting of insects,Arachnida and nematodes. The compounds may be used as pesticides forprotecting crops and in the hygiene, stores protection and veterinarysectors.

Examples of injurious insects from the Lepidoptera order are Plutellamaculipennis, Leucoptera coffeella, Hyponomeuta malinellus, Argyresthiaconjugella, Sitotroga cerealella, Phthorimaea operculella, Capuareticulana, Sparganothis pilleriana, Cacoecia murinana, Tortrixviridana, Clysia ambiguella, Evetria buoliana, Polychrosis botrana,Cydia pomonella, Laspeyresia molesta, Laspeyresia funebra, Ostrinianubilalis, Loxostege sticticalis, Ephestia kuehniella, Chilosuppressalis, Galleria mellonella, Malacosoma neustria, Dendrolimuspini, Thaumatopoea pityocampa, Phalera bucephela, Cheimatobia brumata,Hibernia defoliaria, Bupalus pinarius, Hyphantria cunea, Agrotissegetum, Agrotis ypsilon, Barathra brassicae, Cirphis unipuncta,Prodenia litura, Laphygma exigua, Panolis flammea, Earis insulana,Plusia gamma, Alabama argillacea, Lymantria dispar, Lymantria monacha,Pieris brassicae, and Aporia crataegi;

examples from the Coleoptera order are Blitophaga undata, Melanotuscommunis, Limonius californicus, Agriotes lineatus, Agriotes obscurus,Agrilus sinuatus, Meligethes aeneus, Atomaria linearis, Epilachnavaricestris, Phyllopertha horticola, Popillia japonica, Melolonthamelolontha, Melolontha hippocastani, Amphimallus solstitialis, Criocerisasparagi, Lema melanopus, Leptinotarsa decemlineata, Phaedoncochleariae, Phyllotreta nemorum, Chaetocnema tibialis, Phylloideschrysocephala, Diabrotica 12-punctata, Cassida nebulosa, Bruchus lentis,Bruchus rufimanus, Bruchus pisorum, Sitona lineatus, Otiorrhynchussulcatus, Otiorrhynchus ovatus, Hylobies abietis, Byctiscus betulae,Anthonomus pomorum, Anthonomus grandis, Ceuthorrhynchus assimilis,Ceuthorrhynchus napi, Sitophilus granaria, Anisandrus dispar, Ipstypographus, and Blastophagus piniperda;

examples from the Diptera order are Lycoria pectoralis, Mayetioladestructor, Dasyneura brassicae, Contarinia tritici, Haplodiplosisequestris, Tipula paludosa, Tipula oleracea, Dacus cucurbitae, Dacusoleae, Ceratitis capitata, Rhagoletis cerasi, Rhagoletis pomonella,Anastrepha ludens, Oscinella frit, Phorbia coarctata, Phorbia antiqua,Phorbia brassicae, Pegomya hyoscyami, Anopheles maculipennis, Culexpipiens, Aedes aegypti, Aedes vexans, Tabanus bovinus, Tipula paludosa,Musca domestica, Fannia canicularis, Muscina stabulans, Glossinamorsitans, Oestrus ovis, Chrysomya macellaria, Chrysomya hominivorax,Lucilia cuprina, Lucilia sericata, and Hypoderma lineata;

examples from the Hymenoptera order are Athalia rosae, Hoplocampaminuta, Monomorium pharaonis, Solenopsis geminata, and Atta sexdens;

examples from the Heteroptera order are Nezara viridula, Eurygasterintegriceps, Blissus leucopterus, Dysdercus cingulatus, Dysdercusintermedius, Piesma quadrata, and Lygus pratensis;

examples from the Homoptera order are Perkinsiella saccharicida,Nilaparvata lugens, Empoasca fabae, Psylla mali, Psylla piri,Trialeurodes vaporariorum, Aphis fabae, Aphis pomi, Aphis sambuci,Aphidula nasturtii, Cerosipha gossypii, Sappaphis mali, Sappaphis mala,Dysaphis radicola, Brachycaudus cardui, Brevicoryne brassicae, Phorodonhumuli, Rhopalomyzus ascalonicus, Myzodes persicae, Myzus cerasi,Dysaulacorthum pseudosolani, Acyrthosiphon onobrychis, Macrosiphonrosae, Megoura viciae, Schizoneura lanuginosa, Pemphigus bursarius,Dreyfusia nordmannianae, Dreyfusia piceae, Adelges laricis, and Viteusvitifolii;

examples from the Isoptera order are Reticulitermes lucifugus,Calotermes flavicollis, Leucotermes flavipes, and Termes natalensis;

examples from the Orthoptera order are Forficula auricularia, Achetadomestica, Gryllotalpa gryllotalpa, Tachycines asynamorus, Locustamigratoria, Stauronotus maroccanus, Schistocerca peregrina, Nomadacrisseptemfasciata, Melanoplus spretus, Melanoplus femur-rubrum, Blattaorientalis, Blattella germanica, Periplaneta americana, and Blaberagigantea.

Examples of mites and ticks (Acarina) belonging to the Arachnida classare Tetranychus telarius, Tetranychus pacificus, Paratetranychuspilosus, Bryobia praetiosa, Ixodes ricinus, Ornithodorus moubata,Amblyomma americanum, Dermacentor silvarum, and Boophilus microplus.

Examples from the Nemathelminthes class are root-knot nematodes, e.g.,Meloidogyne icognita, Meloidogyne hapla, and Meloidogyne javanica,cyst-forming nematodes, e.g., Heterodera rostochiensis, Heteroderaschachtii, Heterodera avenae, Heterodera glycines, and Heteroderatrifolii, and stem and leaf eelworms, e.g., Ditylenchus dipsaci,Ditylenchus destructor, Pratylenchus neglectus, Pratylenchus penetrans,Pratylenchus goodeyi, Pratylenchus curvitatus and Tylenchorhynchusdubius, Tylenchorhynchus claytoni, Rotylenchus robustus,Heliocotylenchus multicinctus, Radopholus similis, Belonolaimuslongicaudatus, Longidorus elongatus, and Trichodorus primitivus.

The active ingredients may be applied as such, in the form offormulations or application forms prepared therefrom, e.g., as directlysprayable solutions, powders, suspensions, dispersions, emulsions, oildispersions, pastes, dusts, broadcasting agents, or granules byspraying, atomizing, dusting, broadcasting or watering. The forms ofapplication depend entirely on the purpose for which the agents arebeing used, but they must ensure as fine a distribution of the activeingredients according to the invention as possible.

For the preparation of solutions, emulsions, pastes and oil dispersionsto be sprayed direct, mineral oil fractions of medium to high boilingpoint, such as kerosene or diesel oil, further coal-tar oils, and oilsof vegetable or animal origin, aliphatic, cyclic and aromatichydrocarbons such as benzene, toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalenes and their derivatives suchas methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone,etc., and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes,oil dispersions or wettable powders by adding water. To prepareemulsions, pastes and oil dispersions, the ingredients as such ordissolved in an oil or solvent may be homogenized in water by means ofwetting or dispersing agents, adherents or emulsifiers. Concentrateswhich are suitable for dilution with water may be prepared from activeingredient, wetting agent, adherent, emulsifying or dispersing agent andpossibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of ligninsulfonic acid, naphthalenesulfonic acids,phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkylsulfonates, alkali metal and alkaline earth metal salts ofdibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcoholsulfates, alkali metal and alkaline earth metal salts of fatty acids,salts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof sulfated fatty alcohol glycol ethers, condensation products ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensation products of naphthalene or naphthalenesulfonic acids withphenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acid, silica gels,silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetableproducts such as grain flours, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % byweight of active ingredient.

Examples of formulations are given below.

I. 5 parts by weight of compound no. 1 is intimately mixed with 95 partsby weight of particulate kaolin. A dust is obtained containing 5% byweight of the active ingredient.

II. 30 parts by weight of compound no. 3 is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceof this silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

III. 10 parts by weight of compound no. 7 is dissolved in a mixtureconsisting of 90 parts by weight of xylene, 6 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 2 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 2 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil.

IV. 20 parts by weight of compound no. 9 is dissolved is a mixtureconsisting of 60 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxideand 1 mole of isooctylphenol, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil.

V. 80 parts by weight of compound no. 41 is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid10 parts by weight of the sodium salt of a lignin-sulfonic acid obtainedfrom a sulfite waste liquor, and 7 parts by weight of powdered silicagel, and triturated in a hammer mill.

The active ingredient concentrations in the finished formulations mayvary over a wide range. Generally, they are from 0.0001 to 10, andpreferably from 0.01 to 1, %. The active ingredients may alsosuccessfully be used in the ultra-low-volume (ULV) method, where it ispossible to apply formulations containing more than 95 wt % of activeingredient, or even the active ingredient without additives.

In the open, the amount of active ingredient applied is for example from0.001 to 10, and preferably from 0.1 to 1, kg/ha.

There may be added to the active ingredients (if desired, immediatelybefore use (tankmix)) oils of various types, herbicides, fungicides,other insecticides and bactericides. These agents may be added to theactive ingredients according to the invention in a weight ratio of from1:10 to 10:1.

Examples of active ingredients which may be admixed are as follows:1,2-dibromo-3-chloropropane, 1,3-dichloropropene, 1,3-dichloropropene1,2-dichloropropane, 1,2-dibromethane,2-sec-butylphenyl-N-methylcarbamate, o-chlorophenyl-N-methylcarbamate,3-isopropyl-5-methylphenyl-N-methylcarbamate,o-isopropoxyphenyl-N-methylcarbamate,3,5-dimethyl-4-methylmercaptophenyl-N-methylcarbamate,4-dimethylamino-3,5-xylyl-N-methylcarbamate,2-(1,3-dioxolan-2-yl)-phenyl-N-methylcarbamate,1-naphthyl-N-methylcarbamate,2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate,2,2-dimethyl-1,3-benzodioxol-4-yl-N-methylcarbamate,2-dimethylamino-5,6-dimethyl-4-pyrimidinyldimethylcarbamate,2-methyl-2-(methylthio)-propion aldehyde-O-(methylcarbamoyl)-oxime,S-methyl-N-[(methylcarbamoyl)-oxy]-thioacetimidate,methyl-N',N'-dimethyl-N-[(methylcarbamoyl)-oxy]-1-thiooxamidate,N-(2-methyl-4-chlorophenyl)-N'N'-dimethylformamidine,tetrachlorothiophene, 1-(2,6-difluorobenzyl)-3-(4-chlorophenyl)-urea,O,O-dimethyl-O-(p-nitrophenyl)-phosphorothioate,O,O-diethyl-O-(p-nitrophenyl)-phosphorothioate,O-ethyl-O-(p-nitrophenyl)-phenylphosphonothioate,O,O-dimethyl-O-(3-methyl-4-nitrophenyl)phosphorothioate,O,O-diethyl-O-(2,4-dichlorophenyl)-phosphorothioate,O-ethyl-O-(2,4-dichlorophenyl)-phenylphosphonothioate,O,O-dimethyl-O-(2,4,5-trichlorophenyl)-phosphorothioate,O-ethyl-O-(2,4,5-trichlorophenyl)-ethyl-phosphonothioate,O,O-dimethyl-O-(4-bromo-2,5-dichlorophenyl)-phosphorothioate,O,O-dimethyl-O-(2,5-dichloro-4-iodophenyl)-phosphorothioate,O,O-dimethyl-O-(3-methyl-4-methylthiophenyl)-phosphorothioate,O-ethyl-O-(3-methyl-4-methylthiophenyl)-isopropylphosphoramidate,O,O-diethyl-O-[p-(methylsulfynyl)-phenyl]-phosphorothioate,O-ethyl-S-phenylethyl-phosphonodithioate,O,O-diethyl-[2-chloro-1-(2,4-dichlorophenyl)-vinyl]-phosphate,O,O-dimethyl-[-2-chloro-1-(2,4,5-trichlorophenyl)]-vinylphosphate,O,O-dimethyl-S-(1-phenyl)-ethylacetate phosphoro dithioate,bis-(dimethylamino)-fluorophosphine oxide, octamethyl-pyrophosphoramide,O,O,O,O-tetraethyldithiopyrophosphate,S-chloromethyl-O,O-diethyl-phosphorodithioate,O-ethyl-S,S-dipropyl-phosphorodithioate,O,O-dimethyl-O-2,2-dichlorovinylphosphate,O,O-dimethyl-1,2-dibromo-2,2-dichloroethylphosphate,O,O-dimethyl-2,2,2-trichloro-1-hydroxyethylphosphonate,O,O-dimethyl-S-[1,2-biscarbethoxyethyl-(1)]-phosphorodithioate,O,O-dimethyl-O-(1-methyl-2-carbomethoxyvinyl)-phosphate,O,O-dimethyl-S-(N-methylcarbamoylmethyl)-phosphorodithioate,O,O-dimethyl-S-(N-methylcarbamoylmethyl)-phosphorothioate,O,O-dimethyl-S-(N-methoxyethylcarbamoylmethyl)-phosphorodithioate,O,O-dimethyl-S-(N-formyl-N-methylcarbamoylmethyl)-phosphorodithioate,O,O-dimethyl-O-[1-methyl-2-(methylcarbamoyl)-vinyl]-phosphate,O,O-dimethyl-O-[(1-methyl-2-dimethylcarbamoyl)-vinyl]-phosphate,O,O-dimethyl-O-[(1-methyl-2-chloro-2-diethylcarbamoyl)-vinyl]-phosphate,O,O-diethyl-S-(ethylthiomethyl)-phosphorodithioate,O,O-diethyl-S-[(p-chlorophenylthio)-methyl]-phosphorodithioate,O,O-dimethyl-S-(2-ethylthioethyl)-phosphorothioate,O,O-dimethyl-S-(2-ethylthioethyl)-phosphorodithioate,O,O-dimethyl-S-(2-ethylsulfynylethyl)-phosphorothioate,O,O-diethyl-S-(2-ethylthioethyl)-phosphorodithioate,O,O-diethyl-S-(2-ethylsulfynylethyl)-phosphorothioate,O,O-diethyl-S-(2-ethylsulfynylethyl)-phosphorothioate,O,O-diethylthiophosphoryliminophenyl-acetonitrile,O,O-diethyl-S-(2-chloro-1-phthalimiidoethyl)-phosphorodithioate,O,O-diethyl-S-[6-chlorobenzoxazolon-(2)-yl-(3)]-methyldithiophosphate,O,O-dimethyl-S-[2-methoxy-1,3,4-thiadiazol-5[4H]-only-(4)-methyl]-phosphorodithioate,O,O-diethyl-O-[3,5,6-trichloropyridyl-(2)]-phosphorothioate,O,O-diethyl-O-(2-pyrazinyl)-phosphorothioate,O,O-diethyl-O-[2-isopropyl-4-methylpyrimidinyl-(6)]phosphorothioate,O,O-diethyl-O-[2-(diethylamino)-6-methyl-4-pyrimidinyl]-thionophosphate,O,O-dimethyl-S-(4-oxo-1,2,3-benzotriazin-3[4H]-yl-methyl)-phosphorodithioate,O,O-dimethyl-S-[(4,6-diamino-1,3,5-triazin-2-yl)-methyl]-phosphorodithioate,O,O-diethyl-(1-phenyl-1,2,4-triazol-3-yl)-thionophosphate,O,S-dimethylphosphoroamidothioate,O,S-dimethyl-N-acetylphosphoramidothioate, alpha-hexachlorocyclohexane,1,1-di-(p-methoxyphenyl)-2,2,2-trichloroethane,6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide,pyrethrins,DL-2-allyl-3-methyl-cyclopenten-(2)-on-(1)-yl-(4)-DL-cis,trans-chrysanthemate,5-benzylfuryl-(3)-methyl-DL-cis,trans-chrysanthemate,3-phenoxybenzyl(±)-cis,trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate,alpha-cyano-3-phenoxybenzyl(±)-cis,trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate,(s)-alpha-cyano-3-phenoxybenzyl-cis(1R,3R)-2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropanecarboxylate,3,4,5,6-tetrahydrophthalimidoethyl-DL-cis,trans-chrysanthemate,2-methyl-5-(2-propynyl)-3-furylmethyl-chrysanthemate, andalpha-cyano-3-phenoxybenzyl-alpha-isopropyl-4-chlorophenylacetate.

MANUFACTURING EXAMPLES Example 1N-[(p-phenoxyphenoxy)-methyl]-4,5-dichloroimidazole (compound 1)

94 g of 1-hydroxymethyl-4,5-dichloroimidazole is dissolved in 550 ml ofcarbon tetrachloride. 1 ml of dimethylformamide is added, and 100.5 g ofthionyl chloride is dripped in while stirring. The mixture is refluxeduntil no more gas evolves, after which the solvent is removed underreduced pressure and 750 ml of methylene chloride and 250 ml of waterare added to the residue. While the mixture is stirred thoroughly, itspH is brought to 7.5 with 5% strength aqueous sodium hydroxide solution.The organic phase is then separated, washed with water and dried oversodium sulfate. The residue remaining after removal of the solvent isdistilled at 92° to 95° C./0.1 mbar. There is obtained 80.5 g (77%) of1-chloromethyl-4,5-dichloroimidazole; m.p.: 40°-41° C.

9.3 g of 4-phenoxyphenol is dissolved in 60 ml of anhydrousdimethylformamide. 1.58 g of 80% strength sodium hydride is added, andthe mixture is heated at 60° C. until no more hydrogen evolves (about 1hour). A solution of 9.28 g of N-(1-chloromethyl)-4,5-dichloroimidazolein 30 ml of dimethylformamide is then dripped in. The mixture is stirredovernight at room temperature, after which it is poured into 500 ml ofwater, followed by extraction three times with methyl tert-butyl ether.The combined organic phases are washed three times with water, driedover sodium sulfate, and freed from solvent under reduced pressure. Thesolid residue is recrystallized from n-pentane/ether (6:1) to giveN-[(p-phenoxyphenoxy)-methyl]-4,5-dichloroimidazole, m.p.: 82°-83° C.

C₁₆ H₁₂ Cl₂ N₂ O₂ (335): calc.: C 57.4, H 3.6, N 8.4. found: C 57.7, H3.7, N 8.3.

Infrared absorptions (cm⁻¹): 1478, 1403, 1235, 1209, 1047, 854.

Example 2 N-[p-(3-chlorophenoxy)-benzyl]-4,5-dimethylimidazole (compound2)

While stirring thoroughly, 1.91 g of 80% strength sodium hydride isintroduced into a solution of 6.04 g of 4,5-dimethylimidazole in 80 mlof tetrahydrofuran. Upon completion of the exothermic reaction, themixture is kept for 3 hours at 60° C., and then cooled. A solution of17.85 g of p-(3-chlorophenoxy)-benzyl bromide in 20 ml oftetrahydrofuran is then added. The reaction batch is stirred for 12hours at 20° C., then poured into about 750 ml of ice water andextracted by shaking with methyl tert-butyl ether. The extract is washedtwice with 5% strength aqueous sodium hydroxide solution and twice withwater. After the extract has been dried over sodium sulfate, the solventis removed under reduced pressure and the residue is chromatographedover silica gel 60 with acetone/ethyl acetate (2:1). There is obtained12.1 g (65%) of N-[p-(3-chlorophenoxy)-benzyl]-4,5-dimethylimidazole asa resin-like liquid which slowly crystallizes on standing.

C₁₈ H₁₇ ClN₂ O (312.5): calc.: C 69.1, H 5.5, N 9.0. found: C 69.1, H5.5, N 8.9.

Infrared absorptions (cm⁻¹): 1505, 1474, 1306, 1226, 901.

Example 3 N-[(p-phenoxyphenoxy)-ethyl]-4,5-dichloroimidazole (compound3)

23.0 g of 2-(4-phenoxyphenoxy)-ethanol and 22.9 g of p-toluenesulfonylchloride are dissolved in 100 ml of methylene chloride; 18.96 g ofpyridine is dripped in at from 10° to 15° C. The mixture is stirred for30 minutes at room temperature and for 4 hours under reflux. The solventis then removed under reduced pressure, and the residue is dissolved in150 ml of pyridine and poured into 600 ml of ice water. The solid whichprecipitates is filtered off, dried and recrystallized fromcyclohexane/methyl tert-butyl ether (5:1). There is obtained 28.2 g(73%) of 2-[(p-phenoxyphenoxy)-ethyl] p-toluenesulfonate; m.p.: 53°-55°C.

A mixture of 8.43 g of 4,5-dichloroimidazole, 80 ml of dimethylformamideand 1.83 g of sodium hydride is heated, with stirring, for 3 hours at60° C. Subsequently, a solution of 23.04 g of2-[(p-phenoxyphenoxy)-ethyl] p-toluenesulfonate in 40 ml ofdimethylformamide is dripped in. The mixture is heated for 12 hours at100° C., cooled, poured into 50 ml of ice water, and extracted severaltimes with ethyl acetate, and the combined extracts are washed firstwith 5% strength aqueous sodium hydroxide solution and then with water.Drying over sodium sulfate, removal of the solvent under reducedpressure and recrystallization from methyl tert-butyl ether gives 16.9 g(81%) of N-[(p-phenoxyphenoxy)-ethyl]-4,5-dichloroimidazole; m.p.:89°-91° C.

C₁₇ Cl₂ N₂ O₂ (349): calc.: C 58.5, H 4.0, N 8.0. found: C 58.2, H 4.1,N 7.9.

Infrared absorptions (cm⁻¹): 1489, 1462, 1255, 1214, 1190, 1063, 845.

Example 4 N-[(p-phenoxyphenoxy)-n-propyl]-imidazole (compound 4)

24.4 g of 3-(4-phenoxyphenoxy)-propan-1-ol is added in portions to asolution of 9.5 g of phosphorus tribromide in 65 ml oftetrachloromethane. When the exothermic reaction has subsided, themixture is heated for 4 hours at 40° C. After the mixture has cooled,the solvent is removed under reduced pressure, the residue is dissolvedin 300 ml of methyl tert-butyl ether, and the organic phase is washedthoroughly with water and dried over sodium sulfate. The crude productremaining after removal of the solvent is purified by silica gelfiltration with toluene/methyl tert-butyl ether (2:1). There is obtained20.8 g (67%) of 3-(p-phenoxyphenoxy)-1-bromopropane; m.p.: 54°-55° C.

1.98 g of 80% strength sodium hydride is added in portions to a solutionof 4.25 g of imidazole in 70 ml of dimethylformamide. Upon completion ofhydrogen evolution the mixture is stirred for a further 3 hours at 60°C., after which a solution of 18.42 g of3-[4-(phenoxy)-phenoxy]-1-bromopropane in 40 ml of dimethylformamide isadded. The mixture is heated for 8 hours at 80° C. and then poured into2.5 liters of ice water. The solid which separates out is filtered offin a desiccator, dried over calcium chloride and purified by filtrationover silica gel. There is obtained 14.5 g (82%) ofN-[(p-phenoxyphenoxy)-n-propyl]-imidazole; m.p.: 54.5°-55.5° C.

C₁₈ H₁₈ N₂ O₂ (294): calc.: C 73.4, H 6.2, N 9.5. found: C 73.1, H 6.3,N 9.4.

Infrared absorptions (cm⁻¹): 1489, 1224, 1196, 1166, 1075, 849.

EXAMPLE 5 1-{[p-(3-methyl)-phenoxyphenoxy]-methyl}-1,2,4-triazole(compound no. 135)

At room temperature (about 20° C.), 7.7 g of1-chloromethyl-1,2,4-triazole hydrochloride is added to 10 g ofp-(3-methylphenoxy)-phenol and 20.7 g of potassium carbonate in 60 ml ofanhydrous dimethylformamide. The mixture is then stirred for 6 hours at70° C. and overnight at room temperature (about 20° C.). The mixture isthen poured into 300 ml of water, followed by extraction three timeswith methyl tert-butyl ether. The combined organic phases are washedthree times with water, dried over sodium sulfate and concentrated. Theresidue is purified by chromatography over silica gel usingtoluene/methyl tert-butyl ether (2:1) as eluant. There is obtained 5.1 gof 1-{[p-(3-methyl)-phenoxyphenoxy]-methyl}-1,2,4-triazole; m.p.:52°-54° C.

EXAMPLE 6 2-Chloro-1-[(p-phenoxyphenoxy)-methyl]-1,3,4-triazole(compound no. 177)

5.6 g of p-phenoxyphenol and 4.2 g of potassium carbonate are heated for1 hour at 70° C. in 50 ml of anhydrous dimethylformamide. Subsequently,5.6 g of 2-chloro-1-chloromethyl-1,3,4-triazole is added and the mixturestirred for 6 hours at 70° C. and overnight at room temperature (about20° C.). The mixture is then poured into 500 ml of water and extractedthree times with ethyl acetate. The combined organic phases are driedover magnesium sulfate and concentrated. The residue is purified bychromatography over silica gel using n-hexane/ethyl acetate (2:1) aseluant. There is obtained 2.8 g of2-chloro-1-[(p-phenoxyphenoxy)-methyl]-1,3,4-triazole as an oil.

300 MHz NMR in CDCl₃ δ [ppm]: 5.95 (2H), 6.90-7.15 (7H), 7.25-7.38 (2H),8.15 (1H).

EXAMPLE 7 1-[(p-phenoxyphenoxy)-methyl]-benzimidazole (compound no. 213)

At room temperature (about 20° C.) and under a nitrogen blanket, 13.95 gof p-phenoxyphenol in 100 ml of anhydrous dimethylformamide is drippedinto 6.75 g of 80% strength sodium hydride in 50 ml of anhydrousdimethylformamide. Upon completion of hydrogen evolution, the mixture isstirred for 4 hours at 60° C. At 10° C., 15.22 g of1-chloromethylbenzimidazole hydrochloride is then added. The mixture isstirred for 8 hours at 120° C. After concentration under reducedpressure, the residue is taken up in ethyl acetate, and washed threetimes with water and three times with 5% strength aqueous sodiumhydroxide solution. The combined organic phases are dried over sodiumsulfate and concentrated. The residue is recrystallized from diethylether. There is obtained 11.8 g of1-[(p-phenoxyphenoxy)-methyl]-benzimidazole of m.p. 112° C.

The compounds Ia-If listed in Tables 1 to 6 below may be prepared inaccordance with the above directions.

                                      TABLE 1                                     __________________________________________________________________________     ##STR11##                                                                                                   Phys. data                                     Compound No.                                                                          R.sup.1                                                                             R.sup.2                                                                          R.sup.3                                                                         X    R.sup.4                                                                         R.sup.5 = R.sup.6                                                                  [IR absorptions (cm.sup.-1)]                   __________________________________________________________________________     1      H     H  H OCH.sub.2                                                                          H Cl   1478, 1403, 1235, 1209                          2      3-Cl  H  H CH.sub.2                                                                           H CH.sub.3                                                                           1505, 1474, 1306, 1226                          3      H     H  H O(CH.sub.2).sub.2                                                                  H Cl   1489, 1462, 1255, 1214                          4      H     H  H O(CH.sub.2).sub.3                                                                  H H    1489, 1224, 1196, 1166                          5      4-F   H  H CH.sub.2                                                                           H Cl   1250, 1212, 1193, 1180                          6      4-OCH.sub.3                                                                         H  H CH.sub.2                                                                           H CH.sub.3                                                                           1443, 1228, 1034                                7      4-Cl  H  H CH.sub.2                                                                           H CH.sub.3                                                                           1240, 1167, 1089                                8      4-Cl  H  H CH.sub.2                                                                           H Cl   1244, 1168, 1098, 1018                          9      3-Cl  H  H CH.sub.2                                                                           H Cl   1471, 1238, 1169                               10      H     H  H CH.sub.2                                                                           H Cl   1242, 1169, 983                                11      H     H  H CH.sub.2                                                                           H CH.sub.3                                                                           1447, 1237, 1167                               12      4-NO.sub.2                                                                          H  H CH.sub.2                                                                           H CH.sub.3                                                                           1336, 1248, 1201, 1189                         13      4-NO.sub.2                                                                          H  H CH.sub.2                                                                           H Cl   1338, 1247, 1202, 1167                         14      4-F   H  H CH.sub.2                                                                           H CH.sub.3                                                                           1253, 1213,                                    15      4-C.sub.2 H.sub.5                                                                   H  H CH.sub.2                                                                           H Cl   1245, 1170, 982                                16      4-OCH.sub.3                                                                         H  H CH.sub.2                                                                           H Cl   1250, 1169, 1033                               17      4-CH.sub.3                                                                          H  H CH.sub.2                                                                           H Cl   1248, 1172                                     18      4-CH.sub.3                                                                          H  H CH.sub.2                                                                           H CH.sub.3                                                                           1241, 1171                                     19      4-C.sub.2 H.sub.5                                                                   H  H CH.sub.2                                                                           H CH.sub.3                                                                           1447, 1238, 1169                               20      H     H  H CH.sub.2                                                                           H Cl                                                  21      3-CF.sub.3                                                                          H  H CH.sub.2                                                                           H Cl                                                  22      3-F   4-F                                                                              H CH.sub.2                                                                           H Cl                                                  23      4-CF.sub.3                                                                          H  H CH.sub.2                                                                           H Cl                                                  24      H     H  H CH.sub.2                                                                           Br                                                                              Cl                                                  25      H     H  H CH.sub.2                                                                           Cl                                                                              Cl                                                  26      H     H  H O(CH.sub.2).sub.2                                                                  H CH.sub.3                                                                           1447, 1254, 1220, 1059                         27      H     H  H O(CH.sub.2).sub.2                                                                  H H    1460, 1231, 1218, 1108                         28      3-F   H  H O(CH.sub.2).sub.2                                                                  H Cl                                                  29      3-Cl  H  H O(CH.sub.2).sub.2                                                                  H Cl                                                  30      3-CF.sub.3                                                                          H  H O(CH.sub.2).sub.2                                                                  H Cl                                                  31      3-F   4-F                                                                              H O(CH.sub.2).sub.2                                                                  H Cl                                                  32      4-CF.sub.3                                                                          H  H O(CH.sub.2).sub.2                                                                  H Cl                                                  33      3-CH.sub.3                                                                          H  H O(CH.sub.2).sub.2                                                                  H Cl                                                  34      H     H  H O(CH.sub.2).sub.2                                                                  Cl                                                                              Cl                                                  35      3-Cl  H  H O(CH.sub.2).sub.2                                                                  Cl                                                                              Cl                                                  36      H     H  H O(CH.sub.2).sub.2                                                                  Br                                                                              Cl                                                  37      3-Cl  H  H O(CH.sub.2).sub.2                                                                  Br                                                                              Cl                                                  38      3-F   H  H O(CH.sub.2).sub.2                                                                  Br                                                                              Cl                                                  39      3-CF.sub.3                                                                          H  H O(CH.sub.2).sub.2                                                                  Br                                                                              Cl                                                  40      3-F   4-F                                                                              H O(CH.sub.2).sub.2                                                                  Br                                                                              Cl                                                  41      H     H  H O(CH.sub.2).sub.3                                                                  H Cl   1258, 1250, 1219, 1191                         42      H     H  H O(CH.sub.2).sub.2                                                                  H CH.sub.3                                                                           1473, 1220, 1186                               43      4-F   H  H O(CH.sub.2).sub.2                                                                  H Cl                                                  44      4-F   H  H OCH.sub.2                                                                          H Cl   1483, 1205, 1116, 1035                         45      4-Cl  H  H OCH.sub.2                                                                          H Cl   1472, 1240, 1212, 1186                         46      3-CF.sub.3                                                                          H  H OCH.sub.2                                                                          H Cl   1329, 1213, 1185, 1125                         47      4-CH.sub.3                                                                          H  H OCH.sub.2                                                                          H Cl   1501, 1255, 1244, 1203                         48      3-F   4-F                                                                              H OCH.sub.2                                                                          H Cl   1250, 1225, 1203, 1187                         49      4-F   H  H OCH.sub.2                                                                          H Cl   1496, 1403, 1236, 1230                         50      4-CF.sub.3                                                                          H  H OCH.sub.2                                                                          H Cl                                                  51      H     H  H OCH.sub.2                                                                          Br                                                                              Cl                                                  52      4-Cl  H  H OCH.sub.2                                                                          Br                                                                              Cl                                                  53      3-F   H  H OCH.sub.2                                                                          Br                                                                              Cl                                                  54      3-CF.sub.3                                                                          H  H OCH.sub.2                                                                          Br                                                                              Cl                                                  55      3-CH.sub.3                                                                          H  H OCH.sub.2                                                                          Br                                                                              Cl                                                  56      4-F   H  H OCH.sub.2                                                                          Br                                                                              Cl                                                  57      4-CF.sub.3                                                                          H  H OCH.sub.2                                                                          Br                                                                              Cl                                                  58      4-Cl  H  H OCH.sub.2                                                                          Br                                                                              Cl                                                  59      3-F   4-F                                                                              H OCH.sub.2                                                                          Br                                                                              Cl                                                  60      H     H  H OCH.sub.2                                                                          Cl                                                                              Cl                                                  61      3-Cl  H  H OCH.sub.2                                                                          Cl                                                                              Cl                                                  62      3-F   H  H OCH.sub.2                                                                          Cl                                                                              Cl                                                  63      3-CF.sub.3                                                                          H  H OCH.sub.2                                                                          Cl                                                                              Cl                                                  64      4-F   H  H OCH.sub.2                                                                          Cl                                                                              Cl                                                  65      4-CF.sub.3                                                                          H  H OCH.sub.2                                                                          Cl                                                                              Cl                                                  66      4-Cl  H  H OCH.sub.2                                                                          Cl                                                                              Cl                                                  67      3-Cl  H  H O(CH.sub.2).sub.3                                                                  H Cl                                                  68      4-F   H  H O(CH.sub.2).sub.3                                                                  H Cl                                                  69      4-CF.sub.3                                                                          H  H O(CH.sub.2).sub.3                                                                  H Cl                                                  70      4-CH.sub.3                                                                          H  H O(CH.sub.2).sub.3                                                                  H Cl                                                  71      3-F   4-F                                                                              H O(CH.sub.2).sub.3                                                                  H Cl                                                  72      4-F   H  H O(CH.sub.2).sub.3                                                                  H Cl                                                  73      4-Cl  H  H O(CH.sub.2).sub.3                                                                  H Cl                                                  74      H     H  H O(CH.sub.2).sub.3                                                                  Cl                                                                              Cl                                                  75      H     H  H O(CH.sub.2).sub.3                                                                  Br                                                                              Cl                                                  76      3-Cl  H  H O(CH.sub.2).sub.3                                                                  Cl                                                                              Cl                                                  77      3-Cl  H  H O(CH.sub.2).sub.3                                                                  Br                                                                              Cl                                                  78      3-F   H  H O(CH.sub.2).sub.3                                                                  Br                                                                              Cl                                                  79      3-F   H  H O(CH.sub.2).sub.3                                                                  Cl                                                                              Cl                                                  80      3-Br  H  H OCH.sub.2                                                                          H Cl   1490, 1470, 1402, 1237                         81      4-Cl  H  H OCH.sub.2                                                                          H Cl   1502, 1489, 1253, 1245                         82      4-Br  H  H OCH.sub.2                                                                          H Cl   1486, 1244, 1206, 1183                         83      4-CH.sub.3                                                                          H  H OCH.sub.2                                                                          H Cl   1501, 1257, 1245, 1204                         84      4-C.sub.2 H.sub.5                                                                   H  H OCH.sub.2                                                                          H Cl   1498, 1242, 1206, 1186                         85      4-F   H  H OCH.sub.2                                                                          H Cl   1481, 1244, 1221, 1203                         86      3-Cl  4-Cl                                                                             H OCH.sub.2                                                                          H Cl   1502, 1468, 1255, 1244                         87      4-tert-C.sub.4 H.sub.9                                                              H  H OCH.sub.2                                                                          H Cl   1501, 1481, 1406, 1231                         88      4-OCH.sub.3                                                                         H  H OCH.sub.2                                                                          H Cl   1498, 1489, 1405, 1236                         89      4-OC.sub.2 H.sub.5                                                                  H  H OCH.sub.2                                                                          H H    1498, 1490, 1405, 1239                         90      H     H  H OCH.sub.2                                                                          H H    1487, 1403, 1213, 1019                         91      3-F   H  H OCH.sub.2                                                                          H H    1485, 1271, 1291, 1204                         92      3-Cl  H  H OCH.sub.2                                                                          H H    1485, 1227, 1214, 1191                         93      3-Br  H  H OCH.sub.2                                                                          H H    1470, 1226, 1213, 1073                         94      3-CH.sub.3                                                                          H  H OCH.sub.2                                                                          H H    1487, 1255, 1221, 1205                         95      H     H  H OCH.sub.2                                                                          H CH.sub.3                                                                           1489, 1406, 1208, 1165                         96      3-F   H  H OCH.sub.2                                                                          H CH.sub.3                                                                           1485, 1271, 1231, 1204                         97      3-Cl  H  H OCH.sub.2                                                                          H CH.sub.3                                                                           1497, 1472, 1231, 1212                         98      3-Br  H  H OCH.sub.2                                                                          H CH.sub.3                                                                           1470, 1424, 1224, 1208                         99      3-CH.sub.3                                                                          H  H OCH.sub.2                                                                          H CH.sub.3                                                                           1499, 1403, 1233, 1211                         100     3-tert-C.sub.4 H.sub.9                                                              H  H OCH.sub.2                                                                          H CH.sub.3                                                                           1403, 1271, 1235, 1214                         __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR12##                                                                    Compound                                                                      No.     R.sup.1  R.sup.2                                                                              R.sup.3                                                                           R.sup.7                                                                            R.sup.8                                                                           R.sup.9                                                                            Phys. data                          ______________________________________                                        101     H        H      H   H    H   H                                        102     3-F      H      H   H    H   H                                        103     3-Cl     H      H   H    H   H                                        104     3-Br     H      H   H    H   H                                        105     3-CF.sub.3                                                                             H      H   H    H   H                                        106     3-CH.sub.3                                                                             H      H   H    H   H                                        107     3-C.sub.2 H.sub.5                                                                      H      H   H    H   H                                        108     3-OCH.sub.3                                                                            H      H   H    H   H                                        109     3-Cl     4-F    H   H    H   H                                        110     H        H      H   CH.sub.3                                                                           H   H                                        111     3-F      H      H   CH.sub.3                                                                           H   H                                        112     3-Cl     H      H   CH.sub.3                                                                           H   H                                        113     3-Br     H      H   CH.sub.3                                                                           H   H                                        114     3-CF.sub.3                                                                             H      H   CH.sub.3                                                                           H   H                                        115     3-CH.sub.3                                                                             H      H   CH.sub.3                                                                           H   H                                        116     3-C.sub.2 H.sub.5                                                                      H      H   CH.sub.3                                                                           H   H                                        117     3-OCH.sub.3                                                                            H      H   CH.sub.3                                                                           H   H                                        118     3-Cl     4-F    H   CH.sub.3                                                                           H   H                                        119     H        H      H   CH.sub.3                                                                           H   CH.sub.3                                                                           300 MHz-                                                                      .sup.1 H-NMR in                                                               CDCl.sub.3 [ppm]:                                                             5.81 (s)                            120     3-F      H      H   CH.sub.3                                                                           H   CH.sub.3                                 121     3-Cl     H      H   CH.sub.3                                                                           H   CH.sub.3                                 122     3-Br     H      H   CH.sub.3                                                                           H   CH.sub.3                                 123     3-CF.sub.3                                                                             H      H   CH.sub.3                                                                           H   CH.sub.3                                 124     3-CH.sub.3                                                                             H      H   CH.sub.3                                                                           H   CH.sub.3                                 125     3-C.sub.2 H.sub.5                                                                      H      H   CH.sub.3                                                                           H   CH.sub.3                                 126     3-OCH.sub.3                                                                            H      H   CH.sub.3                                                                           H   CH.sub.3                                 127     3-Cl     4-F    H   CH.sub.3                                                                           H   CH.sub.3                                 ______________________________________                                    

                                      TABLE 3                                     __________________________________________________________________________     ##STR13##                                                                    Compound No.                                                                          R.sup.1                                                                             R.sup.2                                                                          R.sup.3                                                                          R.sup.10                                                                         R.sup.11                                                                         Phys. data                                          __________________________________________________________________________    128     H     H  H  H  H  mp.: 66-67° C.                               129     H     H  3-F                                                                              H  H                                                      130     H     H  3-Cl                                                                             H  H                                                      131     3-F   H  H  H  H  mp.: 39-41° C.                               132     3-Cl  H  H  H  H  IR absorptions (cm.sup.-1): 1502, 1472, 1274,                                 1232                                                133     3-Br  H  H  H  H  IR absorptions (cm.sup.-1): 1502, 1469, 1273,                                 1230, 1207                                          134     3-CF.sub.3                                                                          H  H  H  H  IR absorptions (cm.sup.-1): 1503, 1450, 1329,                                 1276                                                135     3-CH.sub.3                                                                          H  H  H  H  mp.: 52-54° C.                               136     3-C.sub.2 H.sub.5                                                                   H  H  H  H  mp.: 39-41° C.                               137     3-tert.-butyl                                                                       H  H  H     IR absorptions (cm.sup.-1): 1502, 1487, 1430,                                 1273, 1231                                          138     3-OCH.sub.3                                                                         H  H  H     IR absorptions (cm.sup.-1): 1502, 1489, 1274,                                 1223, 1206                                          139     3-F   4-F                                                                              H  H  H  mp.: 68-70° C.                               140     3-Cl  4-F                                                                              H  H  H  mp.: 74-75° C.                               141     H     H  3-F                                                                              H  H                                                      142     H     H  3-Cl                                                                             H  H                                                      143     3-F   H  3-Cl                                                                             H  H                                                      144     3-F   H  3-F                                                                              H  H                                                      145     3-Cl  H  3-F                                                                              H  H                                                      146     3-Cl  H  3-Cl                                                                             H  H  IR absorptions (cm.sup.-1): 1586, 1508, 1491,                                 1473, 1274                                          147     3-Br  H  3-F                                                                              H  H                                                      148     3-Br  H  3-Cl                                                                             H  H  IR absorptions (cm.sup.-1): 1583, 1490, 1470,                                 1273, 1260                                          149     3-CF.sub.3                                                                          H  3-F                                                                              H  H                                                      150     3-CF.sub.3                                                                          H  3-Cl                                                                             H  H  IR absorptions (cm.sup.-1): 1509, 1491, 1451,                                 1329, 1275                                          151     3-CH.sub.3                                                                          H  3-F                                                                              H  H                                                      152     3-CH.sub.3                                                                          H  3-Cl                                                                             H  H                                                      153     3-C.sub.2 H.sub.5                                                                   H  3-F                                                                              H  H                                                      154     3-C.sub.2 H.sub.5                                                                   H  3-Cl                                                                             H  H                                                      155     3-OCH.sub.3                                                                         H  3-F                                                                              H  H                                                      156     3-OCH.sub.3                                                                         H  3-Cl                                                                             H  H                                                      157     3-Cl  4-F                                                                              3-F                                                                              H  H                                                      158     3-Cl  4-F                                                                              3-Cl                                                                             H  H                                                      159     H     H  H  CH.sub.3                                                                         CH.sub.3                                               160     3-F   H  H  CH.sub.3                                                                         CH.sub.3                                               161     3-Cl  H  H  CH.sub.3                                                                         CH.sub.3                                               162     3-Br  H  H  CH.sub.3                                                                         CH.sub.3                                               163     3-CF.sub.3                                                                          H  H  CH.sub.3                                                                         CH.sub.3                                               164     3-CH.sub.3                                                                          H  H  CH.sub.3                                                                         CH.sub.3                                               165     3-C.sub.2 H.sub.5                                                                   H  H  CH.sub.3                                                                         CH.sub.3                                               166     3-OCH.sub.3                                                                         H  H  CH.sub.3                                                                         CH.sub.3                                               167     3-Cl  4-F                                                                              H  CH.sub.3                                                                         CH.sub.3                                               __________________________________________________________________________

                  TABLE 4                                                         ______________________________________                                         ##STR14##                                                                    Compound                                                                      No.     R.sup.1 R.sup.2                                                                              R.sup.3                                                                           R.sup.12                                                                           R.sup.13                                                                           Phys. data                               ______________________________________                                        168     H       H      H   H    H                                             169     3-F     H      H   H    H                                             170     3-Cl    H      H   H    H                                             171     3-Br    H      H   H    H                                             172     3-CF.sub.3                                                                            H      H   H    H                                             173     3-CH.sub.3                                                                            H      H   H    H                                             174     3-C.sub.2 H.sub.5                                                                     H      H   H    H                                             175     3-OCH.sub.3                                                                           H      H   H    H                                             176     3-Cl    4-F    H   H    H                                             177     H       H      H   H    Cl   300 MHz-.sup.1 H-NMR                                                          in CDCl.sub.3 [ppm]:                                                          5.95 (s)                                 178     3-F     H      H   H    Cl                                            179     3-Cl    H      H   H    Cl                                            180     3-Br    H      H   H    Cl   300 MHz-.sup.1 H-NMR                                                          in CDCl.sub.3 [ppm]:                                                          8.21 (s)                                 181     3-CF.sub.3                                                                            H      H   H    Cl   300 MHz-.sup.1 H-NMR                                                          in CDCl.sub.3 [ppm]:                                                          5.97 (s)                                 182     3-CH.sub.3                                                                            H      H   H    Cl   mp.: 59-62° C.                    183     3-C.sub.2 H.sub.5                                                                     H      H   H    Cl                                            184     3-OCH.sub.3                                                                           H      H   H    Cl                                            185     3-Cl    4-F    H   H    Cl                                            186     H       H      H   CH.sub.3                                                                           CH.sub.3                                      187     3-F     H      H   CH.sub.3                                                                           CH.sub.3                                      188     3-Cl    H      H   CH.sub.3                                                                           CH.sub.3                                      189     3-Br    H      H   CH.sub.3                                                                           CH.sub.3                                      190     3-CF.sub.3                                                                            H      H   CH.sub.3                                                                           CH.sub.3                                      191     3-CH.sub.3                                                                            H      H   CH.sub.3                                                                           CH.sub.3                                      192     3-C.sub.2 H.sub.5                                                                     H      H   CH.sub.3                                                                           CH.sub.3                                      193     3-OCH.sub.3                                                                           H      H   CH.sub.3                                                                           CH.sub.3                                      194     3-Cl    4-F    H   CH.sub.3                                                                           CH.sub.3                                      ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                         ##STR15##                                                                    Compound                                                                      No.     R.sup.1  R.sup.2                                                                              R.sup.3                                                                           R.sup.14                                                                           Phys. data                                   ______________________________________                                        195     H        H      H   H    mp.: 73-74° C.                        196     3-F      H      H   H    mp.: 65-66° C.                        197     3-Cl     H      H   H    mp.: 72-73° C.                        198     3-Br     H      H   H    mp.: 69-71° C.                        199     3-CF.sub.3                                                                             H      H   H                                                 200     3-CH.sub.3                                                                             H      H   H                                                 201     3-C.sub.2 H.sub.5                                                                      H      H   H    300 MHz-.sup.1 H-NMR in                                                       CDCl.sub.3 [ppm]: 6.28 (s)                   202     3-OCH.sub.3                                                                            H      H   H                                                 203     3-Cl     4-F    H   H                                                 204     H        H      H   CH.sub.3                                          205     3-F      H      H   CH.sub.3                                          206     3-Cl     H      H   CH.sub.3                                          207     3-Br     H      H   CH.sub.3                                          208     3-CF.sub.3                                                                             H      H   CH.sub.3                                          209     3-CH.sub.3                                                                             H      H   CH.sub.3                                          210     3-C.sub.2 H.sub.5                                                                      H      H   CH.sub.3                                          211     3-OCH.sub.3                                                                            H      H   CH.sub.3                                          212     3-Cl     4-F    H   CH.sub.3                                          ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                         ##STR16##                                                                    Compound                                                                      No.      R.sup.1  R.sup.2 R.sup.3                                                                            R.sup.15                                                                            Phys. data                               ______________________________________                                        213      H        H       H    H     mp.: 112° C.                      214      3-F      H       H    H     mp.: 112° C.                      215      3-Cl     H       H    H     mp.: 99° C.                       216      3-Br     H       H    H     mp.: 100° C.                      217      3-CF.sub.3                                                                             H       H    H                                              218      3-CH.sub.3                                                                             H       H    H     mp.: 108° C.                      219      3-C.sub.2 H.sub.5                                                                      H       H    H                                              220      3-OCH.sub.3                                                                            H       H    H     mp.: 156° C.                      221      3-Cl     4-F     H    H     mp.: 111° C.                      222      H        H       3-Cl H                                              223      H        H       3-F  H                                              224      3-F      H       3-Cl H                                              225      3-Cl     H       3-F  H                                              226      3-Br     H       3-Cl H                                              227      3-CF.sub.3                                                                             H       3-F  H                                              228      3-CH.sub.3                                                                             H       3-Cl H                                              229      3-C.sub.2 H.sub.5                                                                      H       3-F  H                                              230      3-OCH.sub.3                                                                            H       3-Cl H                                              231      3-Cl     4-F     3-F  H                                              232      H        H       H    CH.sub.3                                                                            mp.: 127° C.                      233      3-F      H       H    CH.sub.3                                                                            mp.: 129° C.                      234      3-Cl     H       H    CH.sub.3                                                                            mp.: 95° C.                       235      3-Br     H       H    CH.sub.3                                                                            mp.: 82° C.                       236      3-CF.sub.3                                                                             H       H    CH.sub.3                                       237      3-CH.sub.3                                                                             H       H    CH.sub.3                                                                            mp.: 114° C.                      238      3-C.sub.2 H.sub.5                                                                      H       H    CH.sub.3                                       239      3-OCH.sub.3                                                                            H       H    CH.sub.3                                       240      3-Cl     4-F     H    CH.sub.3                                                                            mp.: 94° C.                       241      H        H       3-Cl CH.sub.3                                       242      H        H       3-F  CH.sub.3                                       243      3-F      H       3-Cl CH.sub.3                                       244      3-Cl     H       3-F  CH.sub.3                                       245      3-Br     H       3-Cl CH.sub.3                                       246      3-CF.sub.3                                                                             H       3-F  CH.sub.3                                       247      3-CH.sub.3                                                                             H       3-Cl CH.sub.3                                       248      3-C.sub.2 H.sub.5                                                                      H       3-F  CH.sub.3                                       249      3-OCH.sub.3                                                                            H       3-Cl CH.sub.3                                       250      3-Cl     4-F     3-F  CH.sub.3                                       ______________________________________                                    

USE EXAMPLES

In the examples below, the action of the compounds according to theinvention, or agents containing them, on pests was compared with that ofthe following prior art compounds: ##STR17##

The concentrations at which the investigated compounds achieve a 100%kill or inhibition are the minimum concentrations. At least onereplicate was used for each concentration.

Example A Dysdercus intermedius (Cotton Stainer); Breeding Experiment

200 g of sterile quartz sand (particle size: 0-3 mm) was introduced into1 liter jars. 20 ml of aqueous formulations of the active ingredientswas poured onto this sand prior to commencement of the experiment. 10larvae of the fourth larval stage were then placed in the jars. The foodproffered was swollen cotton seeds, which were replaced weekly. The sandwas moistened, also weekly, with pure water. The temperature was kept at25° to 27° C. The observation period extended up to pupation of theadults. The sample was considered to be effective when, on completion ofthe experiment, the animals were either dead or in the form of giantlarvae or intermediate types (adultoids), or exhibited extensivemorphological defects.

In this experiment, a 100% kill rate was achieved with≦10 ppm of activeingredients 128, 131, 132, 134 and 177. Comparative agents A, B and Chad no effect at a rate of 10 ppm.

Example B Prodenia litura; Ovicidal Action

Eggs of Prodenia litura laid on parchment and which were not older than24 hours were cut from the paper. 0.5 ml of aqueous formulations of theactive ingredients was then pipetted onto the eggs. The eggs were thenplaced in plastic pallets lined with filter paper. The pallets were thencovered with a glass plate. Assessment took place after about 5 days,when the larvae in the control had emerged.

In this experiment, a quantitative inhibition of hatching was achievedwith≦0.5 wt % of compounds 128, 131, 132, 136, 150 and 232.

Example C Prodenia litura; Breeding Experiment

Breeding took place in 100 ml plastic breakers containing about 50 ml ofthe standard nutrient medium with which the active ingredients had beencarefully mixed while warm. For each concentration, 1 beaker with 5caterpillars of the fourth larval stage was employed. The temperaturewas kept at 25° to 26° C. The experiment was monitored until the mothshatched. The sample was considered to be effective when giant larvaewere produced.

In this experiment, a quantitative action was achieved with≦0.5 ppm ofactive ingredients 132 and 134. Comparative agents A, B and C had noeffect at a rate of 5.0 ppm.

Example D Ovicidal Action on Dysdercus intermedius (Cotton Stainer)

Pieces of adhesive tape (about 0.8 cm) were stuck to the top edge ofplastic plant markers. 24 hours before commencement of the experiment,eggs of the cotton stainer contained in a vessel were attached to theadhesive strips by dipping the markers into the vessel. The eggs werethen dipped for 5 seconds into aqueous formulations of the activeingredients and excess liquid was allowed to drip off onto filter paper,care being taken to prevent the eggs coming into contact with the paper.The markers were then placed in plastic trays (adhesive strip at thetop). Half a roll of absorbent cotton was moistened with water andplaced in each beaker to prevent drying out, and the trays were coveredwith a glass plate. Assessment took place after the control bugs hatched(after about 8 days).

In this experiment, hatching was inhibited most successfully with 0.005wt % of compounds 128, 131, 132, 133 and 139. Comparative agents A, Band C had no effect at 0.1 wt %.

Example E Breeding Experiment with Aedes aegypti (Yellow-fever Mosquito)

At 25° C., 200 ml of tapwater containing the active ingredient wasfilled into 250 ml plastic beakers; 20 to 30 mosquito larvae in thethird to fourth larval stage were then introduced. During theexperiment, a powdered commercial tropical fishfood was fed once.Pupation and hatching of the imagoes, which took place after about 10 to12 days, were assessed.

In this experiment, the lethal dose of compound 7 was 0.5 ppm, and thatof compound 9 and comparative agents A and C 5 ppm.

We claim:
 1. N-substituted azole of the formula I ##STR18## where R¹,R², R³ are each hydrogen, halogen, C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, C₁ -C₄-haloalkyl, C₁ -C₄ -haloalkoxy, C₃ -C₁₀ -cycloalkyl, nitro or cyano,Q isan unsubstituted or substituted azole group of the formulae ##STR19## R⁷to R⁹ denoting hydrogen, halogen, C₁ -C₈ -alkyl, C₁ -C₄ -haloalkyl, C₁-C₄ -alkoxy, C₃ -C₁₀ -cycloalkyl or phenyl or naphthyl which isunsubstituted or mono-, di- or trisubstituted by halogen, C₁ -C₈ -alkyl,C₁ -C₈ -alkoxy, C₁ -C₄ -haloalkyl or C₁ -C₄ -haloalkoxy, and X is --OCH₂--.
 2. A composition for combating insects, mites and nematodescontaining an N-substituted azole as set forth in claim 1, together withconventional carriers.
 3. A composition for combating insects, mites andnematodes as set forth in claim 2, containing from 0.1 to 95 wt % of anN-substituted azole of the formula I.
 4. A process for combatinginsects, arachnids and nematodes, wherein the insects, arachnids andnematodes, or the areas or spaces to be kept free from insects,arachnids and nematodes are treated with a pesticidally effective amountof an N-substituted azole of the formula I as set forth in claim 1.